EP0077624B1 - Synthèse de zéolithes - Google Patents

Synthèse de zéolithes Download PDF

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Publication number
EP0077624B1
EP0077624B1 EP82305369A EP82305369A EP0077624B1 EP 0077624 B1 EP0077624 B1 EP 0077624B1 EP 82305369 A EP82305369 A EP 82305369A EP 82305369 A EP82305369 A EP 82305369A EP 0077624 B1 EP0077624 B1 EP 0077624B1
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Prior art keywords
reaction mixture
rubidium
oxide
zeolite
diamine
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EP0077624A2 (fr
EP0077624A3 (en
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Barrie Milner Lowe
Abraham Araya
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2869—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of other types characterised by an X-ray spectrum and a definite composition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2876—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures from a reacting mixture containing an amine or an organic cation, e.g. a quaternary onium cation-ammonium, phosphonium, stibonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2884—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures the aluminium or the silicon in the network being partly replaced

Definitions

  • the present invention relates to a zeolite synthesis and particularly to a new method for the preparation of zeolite Nu-10.
  • This definition includes both freshly prepared Nu-10 ("freshly prepared” means the product of synthesis, and washing, with optional drying, as hereinafter described) and also forms of it resulting from dehydration, and/or calcination, and/or ion exchange.
  • R may include an alkali metal cation, especially sodium, potassium, rubidium or caesium. Ammonium and hydrogen may also be present.
  • zeolite Nu-10 includes nitrogen-containing organic cations or bases as described below or cationic degradation products thereof, or precursors thereof. These nitrogen containing cations or bases are hereinafter referred to as Q.
  • the freshly prepared Nu-10 may also contain nitrogen-containing compounds well in excess of the 1.5 moles set out in the aforesaid definition of the composition of Nu-10 typically in the range 0.1 to 120 moles per mole of Y 2 0 3 . Since Nu-10 is a zeolite, the nitrogen containing base must be physically trapped within the crystal lattice. It can be removed by thermal treatment and/or oxidative degradation or by displacement by suitable small molecules. This physically trapped basic material does not constitute part of the composition for the purpose of the definition. Thus Nu-10 as made typically has the following molar composition: wherein M is an alkali metal and/or ammonium and can include hydrogen.
  • the aforementioned patent application also describes a method of preparing zeolite Nu-10 which comprises reacting an aqueous mixture containing specified proportions of at least one oxide XO 2 , at least one oxide Y 2 0 3 and at least one polyalkylene polyamine having the formula: wherein each of R 1 and R 2 , independently, represents hydrogen or a C 1 to C 6 alkyl group, x is in the range 2 to 6 and y is in the range 0 to 10 provided that when y is 0, x is in the range 2 to 5, or a degradation product or a precursor of said polyamine.
  • Preferred polyamines include triethylene tetramine and tetraethylene pentamine.
  • zeolite Nu-10 may be prepared from a reaction mixture in which the aforesaid polyamine is omitted and optionally replaced by an organic compound as hereinafter defined.
  • a method for the preparation of zeolite Nu-10 which comprises reacting an aqueous mixture containing sources of at least one oxide X0 2 , at least one oxide Y 2 0 3 where X is silicon and/or germanium and Y is one or more of aluminium, iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, gallium and boron and, optionally, at least one organic compound selected from:
  • the organic compound (a) may be a diamine, an amino-alcohol or a diol or any mixture thereof, for example a mixture of a diamine and a diol.
  • Suitable diamines include compounds of the formula: wherein each of R 3 to R 6 , independently, represents hydrogen or a C 1 to C 6 alkyl group and n has the meaning given above.
  • a particularly useful diamine is hexamethylene diamine.
  • Suitable diols include 1,6-hexanediol.
  • the organic compound (b) is preferably a 5- or 6-membered saturated heterocyclic diamine such as piperazine or triethylene diamine or a mono-amine such as pyrrolidone, piperidine or morpholine.
  • Mixtures of compounds of types (a) and (b) may be used, for example a mixture of hexamethylene diamine and piperazine.
  • alkali metals for use in the method of the invention include sodium, potassium, rubidium and caesium, and mixtures of two or more of these, especially (a) rubidium and sodium, and (b) rubidium and potassium.
  • the preferred oxide X0 2 is silica (Si0 2 ) and the preferred oxide Y 2 0 3 is alumina (AI203).
  • the silica source can be any of those commonly considered for use in synthesising zeolites, for example powdered silica, silicic acid, colloidal silica or dissolved silica.
  • powdered silicas usable are precipitated silica, especially those made by precipitation from an alkali metal silicate solution, such as the type known as "KS 300" made by AKZO, and similar products, aerosil silicas, fume silicas such as "CAB-O-SIL@" M5 and silica gels suitably in grades for use in reinforcing pigments for rubber or silicone rubber.
  • Colloidal silicas of various particle sizes may be used, for example 10 to 15 or 40 to 50 microns (pm), as sold under the Registered Trade Marks "LUDOX”, “NALCOAG” and “SYTON”.
  • the usable dissolved silicas include commercially available waterglass silicates containing 0.5 to 6.0, especially 2.0 to 4.0 mols of Si0 2 per mol of alkali metal oxide, "active" alkali metal silicates as defined in UK Patent 1193254 and silicates made by dissolving silica in alkali metal hydroxide or quaternary ammonium hydroxide or a mixture thereof.
  • the alumina source is most conveniently a soluble aluminate, but aluminium, and aluminium salts, for example the chloride, nitrate or sulphate, an aluminium alkoxide or alumina itself, which should preferably be in a hydrated or hydratable form such as colloidal alumina, pseudoboehmite, boehmite, gamma alumina or the alpha or beta trihydrate.
  • the reaction mixture is usually reacted under autogenous pressure, optionally with added gas, e.g. nitrogen, at a temperature between 85 and 250°C until crystals of zeolite Nu-10 form, which can be from 1 hour to many months depending on the reactant composition and the operating temperature.
  • Preferred reaction temperatures lie in the range 130 to 220°C. Agitation is optional, but is preferable since it assists homogenisation of the reaction mixture and reduces the reaction time. Seeding of the reaction mixture with Nu-10 can also be advantageous.
  • the solid phase is collected on a filter and washed and is then ready for further steps such as drying, calcination and ion-exchange.
  • the product of the reaction contains alkali metal ions, these have to be at least partly removed in order to prepare the catalytically active hydrogen form of Nu-10 and this can be done by ion exchange with an acid, especially a strong mineral acid such as hydrochloric acid or by way of the ammonium compound, made by ion exchange with a solution of an ammonium salt such as ammonium chloride.
  • Ion exchange can be carried out by slurrying once or several times with the ion-exchange solution.
  • the zeolite is usually calcined before ion exchange but this may be effected after ion-exchange or during ion-exchange if the latter is carried out in a number of stages,
  • Zeolite Nu-10 prepared by the method of the invention is useful as a catalyst, for example as a hydrocarbon conversion catalyst and in the conversion of small oxygen-containing organic molecules to hydrocarbons.
  • Other uses for zeolite Nu-10 are set out in our co-pending European patent application No. 82302366.8 (EP-A-65400). It may be employed using the general techniques described in the prior art for zeolite catalysts.
  • An aluminate solution was made by dissolving 1.04 g of alumina trihydrate in a solution of 8.03 g of rubidium hydroxide monohydrate dissolved in 10.0 g of distilled water in a beaker using a hotplate magnetic stirrer.
  • the aluminate solution was then added to a mixture of 24.0 g CAB-O-SIL M5 silica, 15.5 g of hexane-1,6-diamine and 300 g of water.
  • An additional 48 g of water was used to rinse the aluminate solution from the beaker and added to the reaction mixture. The mixture was then stirred until it appeared to be homogeneous.
  • the zeolite was then filtered from the reaction mixture, washed with distilled water and dried at 120°C.
  • samples of zeolite Nu-10 were made using, in turn, sodium, potassium, rubidium and caesium as the alkali metal.
  • the potassium HMD Nu-10 was calcined for 72 hours in air at 550°C and then equilibrated with water vapour over saturated aqueous sodium chloride solution for 8 days.
  • the X-ray diffraction pattern of the calcined product is shown in Table 3.
  • Intermediate values of x do not lead to the formation of other zeolites and it is clear that the presence of very small amounts of rubidium (as low as 2% of the alkali metals present-see Example 19) is sufficient to prevent the formation of ZSM-5.
  • rubidium is so effective in directing the reaction towards the formation of Nu-10 but it seems possible that rubidium is particularly effective in the formation of seed nuclei of Nu-10 and hence it reduces the induction period for Nu-10 formation and in this particular case reduces it below that for ZSM-5.
  • Example 20 The reaction mixture of Example 20 was identical to those of Table 6 but contained no inorganic cations. This mixture did not crystallise after 243 hours, but when potassium hydroxide equivalent to 5K 2 0 was added to the reaction mixture held at 180°C a mixture of Nu-10, ZSM-5 and cristobalite was formed within 15 hours. This is in marked contrast to Example A (Table 6) which gave a form of ZSM-5 from an identical composition.
  • Example A Table 6 which gave a form of ZSM-5 from an identical composition.
  • One reason may be that X-ray amorphous seed nuclei formed in the alkali free reaction mixture but could not grow because of lack of hydroxide ions to depolymerise the aluminosilicate solids.
  • Examples 21 and 22 are analogous to Example 19 which gave Nu-10 together with a trace of cristobalite.
  • Example 21 shows that some Nu-10 can be produced even if the organic component is omitted.
  • Example 23 gave a very crystalline form of Nu-10 and there is little doubt that the combination of sodium and rubidium ions is particularly suitable for crystallisation of Nu-10.
  • Examples 26 and 27 represent two attempts to prepare Nu-10 from an aluminium-free reaction mixture at 180°C and 150°C respectively. Both reactions gave ZSM-48 but Nu-10 was also formed at the lower temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)

Claims (9)

1. Procédé de préparation de la zéolite Nu-10 qui comprend la réaction d'un mélange aqueux contenant des sources d'au moins un oxyde de X02, d'au moins un oxyde Y203, où X représente le silicium et/ou le germanium et Y représente l'un ou plusieurs d'entre l'aluminium, le fer, le chrome, le vanadium, le molybdène, l'arsenic, l'antimoine, le manganèse, le gallium et le bore et, éventuellement, d'au moins un composé organique choisi parmi:
(a) les composés de la formule:
Figure imgb0022
où chacun d'entre L1 et L2 représente indépendamment un radical hydroxyle ou un radical amino éventuellement substitué et n représente un nombre entier de 2 à 20, avec la restriction que lorsque L et L2 représentent tous deux des radicaux amino éventuellement substitués, n représente un nombre entier de 6 à 20, et
(b) les bases hétérocycliques contenant de l'azote, le mélange de réaction ayant la composition molaire:
XO2/Y2O3=10 à 10000,
M1OH/XO2=10-8 à 1,0,
H2O/XO2=10 à 200,
Q/XO2=0 à 4,
M2Z/XO2=0 à 4,0,

où chacun d'entre M1 et M2 représente un métal alcalin ou l'ammonium, Q représente le composé organique, X et Y ont les significations attribuées ci-dessus et Z représente un radical d'acide.
2. Procédé suivant la revendication 1, dans lequel le mélange de réaction a la composition molaire:
XO2/Y2O3=30 à 1500,
M1OH/XO2=10-6 à 0,25,
H20/X02=15 à 60,
Q/XO2=0,1 à 1,0,
M2Z/XO2=0 à 1,0.
3. Procédé suivant la revendication 1 ou 2, dans lequel le mélange de réaction contient une diamine de formule:
Figure imgb0023
où chacun d'entre R3 à Re représente indépendamment un atome d'hydrogène ou radical alcoyle en C1 à Ce et n représente un nombre entier de 6 à 20.
4. Procédé suivant la revendication 3, dans lequel la diamine est l'hexaméthylène diamine.
5. Procédé suivant l'une quelconque des revendications précédentes, dans léquel le mélange de réaction contient du 1,6-hexanediol.
6. Procédé suivant l'une quelconque des revendications précédentes, dans lequel le métal alcalin est choisi entre le sodium, le potassium, le rubidium et le césium.
7. Procédé suivant la revendication 6, dans lequel le mélange de réaction contient un mélange de métaux alcalins choisi entre (a) le rubidium et le sodium et (b) le rubidium et le potassium.
8. Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'oxyde X02 est la silice et l'oxyde Y203 est l'alumine.
9. Procédé suivant l'une quelconque des revendications précédentes, dans lequel la température de réaction est située dans l'intervalle de 130 à 220°C.
EP82305369A 1981-10-21 1982-10-08 Synthèse de zéolithes Expired EP0077624B1 (fr)

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EP0077624A3 EP0077624A3 (en) 1983-10-05
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JP (1) JPS5891033A (fr)
AU (1) AU554995B2 (fr)
DE (1) DE3269856D1 (fr)
NZ (1) NZ202099A (fr)

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Publication number Priority date Publication date Assignee Title
EP2781583A1 (fr) 2013-03-21 2014-09-24 IFP Energies nouvelles Procédé de conversion de charges issues de sources renouvelables mettant en oeuvre un catalyseur comprenant une zeolithe nu-10 et une silice alumine
EP2781497A1 (fr) 2013-03-21 2014-09-24 IFP Energies nouvelles Procédé de conversion de charges issues de sources renouvelables mettant en oeuvre un catalyseur comprenant une zéolithe Nu-10 et une zeolithe ZSM-48

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FR2949476B1 (fr) 2009-09-02 2012-08-03 Inst Francais Du Petrole Procede de conversion de charges issues de sources renouvelables en co-traitement avec une charge petroliere mettant en oeuvre un catalyseur a base de nickel et de molybdene
FR2949475B1 (fr) 2009-09-02 2012-04-20 Inst Francais Du Petrole Procede de conversion de charges issues de sources renouvelables en co-traitement avec une charge petroliere mettant en oeuvre un catalyseur a base de molybdene
FR2951732B1 (fr) 2009-10-27 2012-08-03 Inst Francais Du Petrole Procede d'hydrotraitement de charges issues de sources renouvelables avec chauffe indirecte mettant en oeuvre un catalyseur a base de nickel et de molybdene presentant un rapport atomique particulier
FR2951734B1 (fr) 2009-10-27 2012-08-03 Inst Francais Du Petrole Procede d'hydrotraitement de charges issues de sources renouvelables avec chauffe indirecte
FR2951733B1 (fr) 2009-10-27 2012-08-10 Inst Francais Du Petrole Procede d'hydrotraitement de charges issues de sources renouvelables avec chauffe indirecte mettant en oeuvre un catalyseur a base de molybdene
FR2969642B1 (fr) 2010-12-22 2012-12-28 IFP Energies Nouvelles Production de carburants paraffiniques a partir de matieres renouvelables par un procede d'hydrotraitement en continu
CN103274428A (zh) * 2013-07-01 2013-09-04 中国海洋石油总公司 一种循环利用母液合成纳米Nu-10分子筛的方法
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CN106853972B (zh) * 2015-12-09 2019-11-08 中国石油天然气股份有限公司 一种ton沸石的稳定合成方法
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Publication number Priority date Publication date Assignee Title
EP2781583A1 (fr) 2013-03-21 2014-09-24 IFP Energies nouvelles Procédé de conversion de charges issues de sources renouvelables mettant en oeuvre un catalyseur comprenant une zeolithe nu-10 et une silice alumine
EP2781497A1 (fr) 2013-03-21 2014-09-24 IFP Energies nouvelles Procédé de conversion de charges issues de sources renouvelables mettant en oeuvre un catalyseur comprenant une zéolithe Nu-10 et une zeolithe ZSM-48

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JPH0214287B2 (fr) 1990-04-06
NZ202099A (en) 1986-07-11
US4900528A (en) 1990-02-13
AU8936182A (en) 1983-04-28
DE3269856D1 (en) 1986-04-17
JPS5891033A (ja) 1983-05-30
EP0077624A2 (fr) 1983-04-27
AU554995B2 (en) 1986-09-11
EP0077624A3 (en) 1983-10-05

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